CN1310830C - An improved process for manufacturing highly concentrated hydroxylamine - Google Patents
An improved process for manufacturing highly concentrated hydroxylamine Download PDFInfo
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- CN1310830C CN1310830C CNB028174453A CN02817445A CN1310830C CN 1310830 C CN1310830 C CN 1310830C CN B028174453 A CNB028174453 A CN B028174453A CN 02817445 A CN02817445 A CN 02817445A CN 1310830 C CN1310830 C CN 1310830C
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- ion
- exchange
- azanol
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- hydroxylammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1481—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1445—Preparation of hydoxylamine from its salts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
An improved ion exchange process for manufacturing and concentrating hydroxylamine from an aqueous solution comprising hydroxylammonium ion and counter anions is disclosed. The process involves the use of an aqueous hydroxylamine wash step which assists in controlling the processing temperature and leads to a more concentrated, purified aqueous hydroxylamine solution.
Description
Background of invention
Invention field
The present invention relates to produce the method for azanol, more particularly relate to and utilize ion exchange resin to produce the purification of hydroxylamine free acid and the method for spissated solution.
Description of Related Art
Azanol prepares by Raschig method or its method of modifying industrial, wherein make ammonium nitrite or Sodium Nitrite in the aqueous solution with ammonium bisulfite or sodium bisulfite and sulfurous gas reaction, and the gained stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate is hydrolyzed into mainly contain the solution that sulfuric acid hydroxylammonium, sulfuric acid, ammonium sulfate and/or sodium sulfate add a small amount of corresponding nitrate.This solution is with being used as the azanol source after the ammonia neutralization or from the pure hydroxyl ammonium salt of this mixture.
A kind of method that obtains pure hydroxyl ammonium salt comprise use the synthetic oxime of the mixture cause ketone contain hydroxylammonium, by lean solution separate oxime and with this oxime of inorganic acid hydrolysis with recovery hydroxyl ammonium salt and ketone that can recirculation.This solution uses long-time heating to be hydrolyzed and requires expensive device cause lean solution to separate oxime and hydroxyl ammonium salt is separated with ketone.In addition, the salt of azanol and weak acid or oxidizing acid can not be by the preparation of this method, because these acid are inoperative or the hydroxyl ammonium salt that forms in hydrolytic process is decomposed to the hydrolysis of oxime.Such sour salt can by with in the relative acid and the cold soln of azanol prepare.
Heinz Holsapfel is at Z.Anorg.und Aligem.Chemie, and the 288th volume has been described in the 28th page (1956) by using the anionite-exchange resin cause preparation of hydroxylammonium salts azanol of OH form.This publication does not relate to azanol is separated from contain other cationic solution.Authorize people's such as Wallace T.Thompson United States Patent (USP) 3 as on April 28th, 1970,508,864 disclosed like that, the perchloric acid hydroxylammonium can by make hydroxylammonium salts by anionite-exchange resin by hydroxyl ammonium salt discharge azanol and with perchloric acid neutralize produce or by with the hydroxylammonium ionic adsorption on Zeo-karb and make perchloric acid pass through this resin subsequently to produce.This method is not with azanol and other cation separation.The cationic exchange method by Earl.J.Wheelwright in Industrial EngineeringChemistry Process Design Development (industrial engineering chemistry technological design development), the 16th volume, the 2nd phase (1977), the 220th page of description is used to prepare the nitric acid hydroxylammonium.This method is not with azanol and other cation separation, and gained nitric acid hydroxylammonium solution contains the nitric acid of significant quantity in addition.
The method of other production, recovery and concentrating hydroxylamine solution and nitric acid hydroxylammonium is known in the prior art.United States Patent (USP) 5,213,784 disclose a kind of method of producing spissated purification nitric acid hydroxylammonium.This method comprises that concentration is lower than about 70% nitric acid to be blended in the solution that contains excessive azanol.This method has been avoided the spontaneous decomposition of product.
United States Patent (USP) 4,725,360 disclose a kind of with the method for sulfuric acid hydroxylammonium form by the waste water reclamation azanol.This method comprises that making waste water pass through the strongly-acid ion-exchanger also uses sulfuric acid wash-out and the associating azanol of ion-exchanger subsequently.
United States Patent (USP) 4,202,765 disclose a kind of method of using anionite purification azanol.This method comprise the solution that will contain azanol by cation exchange resin bed and use monovalence amine or hydroxide bases with the azanol desorb of absorption.
Description of the Prior Art prepare the method for azanol and hydroxyl ammonium salt, but still there is demand in azanol from isolating simple, cheapness of the solution that contains ionic pollutent and continuation method to being used for.In addition, also there is very big demand in the method that can produce the hydroxylamine solution that does not contain anionic impurity such as sulfate radical substantially.
Summary of the invention
The present invention relates to a kind of method of producing azanol, more particularly relate to this method of utilizing ion-exchange.In addition, this method is used various processing steps, thereby obtains the strong solution of azanol with pure state.
In order to understand the present invention easily, numbering is enumerated essential characteristic of the present invention and various preferred below
Embodiment.
1. a method of producing azanol comprises the steps:
(a) feed water solution that will comprise hydroxylammonium ion and pollutent infeeds in the container that contains at least a Zeo-karb, forms the resin that the hydroxylammonium ion loads;
(b) washing water are infeeded in the described container washing the resin of described loading, thereby remove described pollutent, form the resin that the hydroxylammonium ion of purifying loads, wherein said washing water and the association of this resin;
(c) before, the aqueous solution that will comprise azanol infeeds in the described container replacing the described associating washing water of part at least from the loading resin of described purification, thereby forms the associating resin of hydroxylamine solution in subsequently desorption procedure (d);
(d) moisture strippant is infeeded in the described container so that the desorb from the described associating resin of described hydroxylammonium ion is got off, thereby form the unconjugated aqueous hydroxylamine that contains;
(e) the washing water charging is infeeded in the described container from described container, removing described unconjugated solution, thereby form the pure and spissated aqueous solution that comprises described azanol.
2. according to top the 1st method, wherein step (a)-(e) is carried out under 50-70 ℃ column temperature.
3. according to top the 1st method, wherein said feed water solution comprises oxammonium sulfate.
4. according to top the 1st method, wherein said resin is the sulfonated Zeo-karb.
5. according to top the 1st method, wherein said strippant is selected from monovalence amine alkali, monovalence hydroxide bases and composition thereof.
6. according to top the 5th method, wherein strippant is an aqueous ammonium hydroxide.
7. according to top the 6th method, the ammonia concentration that wherein said ammonium hydroxide has is 40wt% at least.
8. according to top the 1st method, wherein said container be ion exchange resin column and described moisture strippant and described rinse water in step (d) and the reduced superficial velocity that adds in the described post (e) be lower than 3.5cm/min.
9. according to top the 1st method, comprise that further the metal chelator of 8-dihydroxyl quinoline-2-formic acid and composition thereof is handled described pure and spissated solution with being selected from hexanaphthene diamino tetraacethyl, thiocarbamide, tetramethyl-thiuram disulfide, 4.
10. according to top the 1st method, wherein in step (a)-(e), further handle described container cooling off described container, thereby be 10-70 ℃ the temperature maintenance of described container with the refrigerant that is selected from propylene glycol, ethylene glycol, propylene glycol/water, glycol/water and composition thereof.
11. according to top the 10th method, wherein before described cooling with being selected from hexanaphthene diamino tetraacethyl, thiocarbamide, 4, the described refrigerant of metal chelator pre-treatment of 8-dihydroxyl quinoline-2-formic acid and composition thereof is so that its bind metal ion pollutent and remove described pollutent from described refrigerant.
12. the method according to top the 1st comprises the steps:
(a) feed water solution that will comprise hydroxylammonium ion, hydrogen ion, ammonium ion, metal ion and anionic pollutant infeeds in the ion exchange column that contains at least a sulfonated Zeo-karb;
(b) when the specific conductivity of ion-exchange effluent surpasses 200mMhos/cm, stop the charging of feed water solution and begin water is infeeded in the described ion exchange column, thereby obtain the materials flow of first ion exchange column washing effluent;
(c) when reaching 0mMhos/cm, the specific conductivity of described exchange column effluent stops the water charging of step (b);
(d) before, aqueous hydroxylamine is infeeded in the described ion exchange column all basically water with the described water charging of displacement from described post in subsequently desorption procedure (e);
(e) ammonia concentration is infeeded in the ion exchange column at least 40% ammonium hydroxide aqueous solution;
(f) when being enough to the amount of complete desorb azanol, adding stops the charging of described ammonium hydroxide aqueous solution in ion exchange column;
(g) the rinse water charging is infeeded in the ion exchange column;
(h) rise to 1.085g/cm when effluent density
3Collect from the effusive product materials flow of ion exchange column when above, wherein this product materials flow is substantially pure azanol and the aqueous streams that does not contain anionic pollutant substantially;
(i) when being reduced to, effluent density is lower than 1.075g/cm
3The time stop to collect the product materials flow; With
(j) stop rinse water being infeeded in the ion exchange column.
13. according to top the 12nd method, wherein step (a)-(j) is carried out under 10-70 ℃ column temperature.
14., wherein in step (j), stop the rinse water charging afterwards with circulation technology repeating step (a)-(j) according to the method for top the 12nd production azanol.
15. according to the method for top the 14th production azanol, wherein this method is finished in the continuous simulation moving-bed ion-exchange equipment.
16. according to top the 1st method, use the continuous simulation ion-exchange unit, this equipment comprises at least 5 ion-exchange areas, each ion exchange column is loaded with the sulfonated Zeo-karb, and this method comprises the steps:
(a) feed water solution that will comprise hydroxylammonium ion, hydrogen ion, ammonium ion, metal ion and the anionic pollutant of first concentration infeeds in first ion-exchange area, obtains being loaded with hydroxylammonium ionic sulfonated Zeo-karb;
(b) washing water are infeeded in second ion-exchange area, this second ion-exchange area comprises and is loaded with hydroxylammonium ionic sulfonated Zeo-karb, obtains the materials flow of first ion exchange column washing effluent;
(c) aqueous hydroxylamine is infeeded in the 3rd ion-exchange area, the 3rd ion-exchange area comprises and the associating sulfonated Zeo-karb of water, obtains the second ion-exchange effluent materials flow;
(d) ammonia concentration is infeeded in the 4th ion-exchange area at least 40% ammonium hydroxide aqueous solution, the 4th ion-exchange area comprises to associate hydroxylammonium ionic sulfonated Zeo-karb, and collects the effluent of the 3rd ion-exchange area;
(e) the rinse water charging is infeeded in the 5th ion-exchange area, obtain the 4th ion-exchange area product materials flow; With
(f) rise to 1.085g/cm when effluent density
3Collect the 4th ion-exchange area effluent materials flow when above, and reduce to 1.075g/cm in effluent density
3The time stop to collect the 4th ion-exchange area effluent materials flow, obtain the moisture azanol product that has the second azanol concentration and do not comprise anionic pollutant substantially, this second azanol concentration is greater than the first azanol concentration in the described feed water solution.
17., wherein use anionite-exchange resin that the azanol product is carried out aftertreatment according to top the 1st, 12 or 16 method.
Description of drawings
To be more readily understood the present invention with reference to following accompanying drawing and in conjunction with describing in detail, wherein:
Fig. 1 is the azanol (HA) and the NH of 1 inch ion exchange column used according to the invention
3The effluent concentration graphic representation;
Azanol (HA) production concentration and the graphic representation of time of Fig. 2 for obtaining according to the present invention, the influence of its reflection HA aqueous solution recirculation step;
Fig. 3 is used according to the invention and inner column temperature in time graphic representation in production HA process when not using recirculation HA solution;
Fig. 4 is the graphic representation of the effluent concentration feature of HA produced according to the invention;
Fig. 5 is the graphic representation of explanation CDTA stablizer to the influence of the self-heating speed of 57wt%HA solution.
Detailed Description Of The Invention
The present invention relates to a kind of by comprising hydroxylammonium ion and ionic pollutant such as H+、NH
4 +, metal and sulfate ion the aqueous solution produce the ion-exchange process of azanol.
Ion-exchange process of the present invention can be used for producing highly pure aqueous hydroxylamine solutions, and the latter is subsequently for the production of azanol salt such as HAN and HAS, and other is used for the azanol salt of various middle purposes and final use. The additional advantages of the inventive method is that it can produce substantially the not moisture azanol product of the purification of cation pollutant and anionic pollutant such as sulfate ion. Term used herein " does not substantially contain " and refers to that the moisture azanol product of purifying has anionic pollutant such as the sulfate radical that is lower than 400ppm, preferred 200ppm or lower anionic pollutant. The term that is used for describing ionic pollutant " does not substantially contain " and refers to that the ionic pollutant that comprises all metal cations is lower than 200ppb.
Ion-exchange process of the present invention can be used for being purified and concentrating hydroxylamine by the hydroxylammonium ion with produced in several ways. These methods for example disclosure and description in United States Patent (USP) 5,213,784 and 4,491, in 567, these two pieces of patents described for the production of the method for hydroxylammonium ion salt such as nitric acid hydroxylammonium (HAN) and sulfuric acid hydroxylammonium (HAS) and in being incorporated herein comprehensively as a reference. The common methods that preparation contains the solution of hydroxylammonium ion is the Raschig method. The Raschig method is produced the aqueous solution that comprises hydroxylammonium ion, hydrogen ion, ammonium ion and sulfate radical.
The inventive method can be used for being purified and the concentrated azanol aqueous solution by any aqueous solution production that contains the hydroxylammonium ion, and former solution includes but not limited to Raschig solution, HAN solution and HAS solution. Yet the inventive method usually just is described by the aqueous solution product that contains the hydroxylammonium ion of Raschig method and HAS purified solution and concentrating hydroxylamine.
The inventive method is used at the container ion exchange resin in the pillar container for example, and this container is loaded with cationic ion-exchange resin with the purification of finishing azanol in conjunction with the hydroxylammonium ion and concentrated. Select suitable cationic ion-exchange resin. All types of cationic ion-exchange resins all are suitable, for example sulfonic acid type, phosphatic type or carboxylic acid type. Sulfonic resin is preferred, because they selectively are higher than other cation and anion to the hydroxylammonium ion.
In ion-exchange process of the present invention, must be contained in the desorb of hydroxylammonium ion from this resin in the exchanger resin. This is usually by using suitable aqueous slkali such as NaOH, potassium hydroxide, Ammonia etc. to finish, and this solution is higher than affinity to azanol to the affinity of cationic ion-exchange resin.
For from resin displacing hydroxylammonium ion, can use any water-soluble monovalence amine or hydroxide bases. Polyacidic base is not too suitable, because their cation has high affinity and thereby can not be easily by the hydroxylammonium ion exchange in ion-exchange loaded cycle subsequently to the exchange site of resin cation. Suitable monoacidic base comprises such as NaOH, potassium hydroxide, lithium hydroxide etc.; Methyl amine, ethylamine, dimethyl amine, diethylamide etc. Preferred alkali is ammonium hydroxide, its advantage be cheap, nontoxic, molecular weight is low and have volatility. In addition, the accessory substance that obtains when the mixture that uses the ammonia conduct by sulfate reclaims the alkali of azanol is ammonium sulfate, and it is valuable fertilizer. Most preferred strippant alkali is that ammonia concentration is at least 30%, preferred at least 40% ammonia spirit.
The ammonia emission permission uses a little excess of ammonia to replace azanol fully from resin, because a small amount of ammonia of pollution products azanol (being lower than about 3%) can easily be removed by evaporation in this operating process in desorption procedure. In addition, any product that is polluted by the ammonium ion of unacceptable content can be recycled and feeds in the incoming flow. Yet, have been found that the azanol solution that can use ammonia displacement azanol in shortage and directly from resin, obtain substantially not containing ammonia and ionic pollutant.
Being used for from the ion exchange resin the aqueous alkali of desorb azanol in desorption procedure can choose wantonly and contain azanol. When this aqueous alkali comprises azanol, the concentration that the azanol concentration that contains by the ion-exchange effluent that finally obtains with the water rinse resin bed subsequently obtains when being significantly higher than and not having azanol in the aqueous alkali. This effect allows in circulation and/or continuous ionic exchange process by simply part azanol product solution being reclaimed denseer azanol solution with the discharging step that is recycled to next circulation after alkali mixes.
Ion-exchange process of the present invention carries out with five steps substantially. Two steps that begin most are defined as " load step " and are comprised of following steps: (1) ion-exchange step, wherein will contain the solution of hydroxylammonium ion by cationic ion-exchange resin, so that the hydroxylammonium ion is combined with cationic ion-exchange resin; (2) washing step wherein imports deionized water or certain other wash solution in the cationic ion-exchange resin, so that hydroxylammonium ion and cationic ion-exchange resin associate to greatest extent. Water-washing step is also with any not ionic pollutant such as hydrogen ion, ammonium ion and anionic pollutant such as the sulfate anion of exchange, and metal ion, as removing in the solution from be filled in the space between the cationic ion-exchange resin particle such as calcium ion, sodium ion, ferrous ion and iron ion, namely with resin " association ". In addition, washings also are used in the temperature that desorption procedure is subsequently before regulated resin column.
Following step is that temperature is kept step and concentration improves step, and the latter comprises with the solution washing resin column of azanol (HA) at least part of from the water in the water in the resin hole and the space between resin particle to replace. Have been found that in order to obtain concentration greater than the pure HA aqueous solution of 12-13%, must use recirculation HA and introduce highly concentrated strippant. Heat release when diluting because of strippant uses highly concentrated strippant with the rising desorption temperature. Use recirculation HA will keep processing temperature, namely the temperature of resin column is 50-80 ℃ to the maximum in whole process. If keep this temperature, then the pure HA product of the thermal decomposition minimum of gained HA and gained obtains with the aqueous solution that surpasses 50wt%.
In addition, it should also be noted that the control to temperature, for example be controlled to be 50-80 ℃, preventing the decomposition of gained HA, thereby cause purer product. At last, utilize moisture HA recirculation step carrying out subsequently hydroxylammonium ion technological temperature of having kept as described below during desorb from the resin. This desorb relates to the heat release of exchange, and therefore this exchange is regulated by moisture HA recirculation.
The aqueous solution that it should be noted HA obtains by a part of azanol product is recycled after following discharging step usually.
The final step of the method is known as " discharging step ". The discharging step is: (4) desorption procedure; (5) rinse step. As previously mentioned, desorption procedure is utilized strong lye solution, and this solution comprises soluble amine or the hydroxide bases that the affinity of cationic ion-exchange resin is higher than the hydroxylammonium ion. Hydroxylammonium ion on this soluble amine or the hydroxide bases displacement resin cation, thereby desorb azanol and it can be collected in ion-exchange effluent material stream. Rinse step is come the azanol of wash-out desorb from the ion exchange column after desorption procedure and with deionized water or certain other washings solution, wherein azanol is to purify and concentrated collection of products. Rinse step is also fully cleaned resin bed so that between strippant or eluted product and the charging subsequently liquid phase reactor does not occur.
What should emphasize is, different from former ion-exchange process, the impurity metal ion that the moisture HA product of gained contains is about 10-20ppb or lower, and the resulting product of other method contains the 5ppm that has an appointment. In addition, different from other ion-exchange process as previously mentioned, the concentration of this product is 50wt% or higher, and the concentration of other method is 12-13wt%.
Be described in more detail below each step.
Ion-exchange step
The feedstock solution that will comprise hydroxylammonium ion and ionic impurity such as sulfate radical or nitrate anion impurity in ion-exchange step feeds in the cation exchange resin column also to be passed through therein. Feedstock solution can comprise other ionic pollutant such as hydrogen ion, ammonium ion, metal ion, sulfate ion, nitrate ion, chlorion and phosphate anion. The type of existing charging pollutant and amount depend on the method for the production of the charging that contains the hydroxylammonium ion greatly. Yet, usually will comprise 20-40wt% hydroxylammonium salt, also pass through therein in the feed water solution infeed resin column such as 30-35wt% sulfuric acid hydroxylammonium (HAS), be loaded with the resin of azanol with formation.
The hydroxylammonium ion that feeds in the resin filling post is kept by cationic ion-exchange resin, until this resin is at least part of saturated by the hydroxylammonium ion, the hydroxylammonium ion began to appear in the effluent and reached and spills this moment. Load resin with the hydroxylammonium ion and shown the maximum that from feedstock solution, quantitatively to remove and to make simultaneously the hydroxylammonium ion of the loss reduction of hydroxylammonium ion in the effluent of this exchange step by cationic ion-exchange resin until reach the first method of breakthrough point. After spilling, the generation azanol continues the hydroxylammonium ion is fed to the second method that has represented the resin loading in the resin filling post, wherein the hydroxylammonium ion appears in the effluent material stream, until the molar fraction of hydroxylammonium ion in effluent reaches the molar fraction of hydroxylammonium ion in feedstock solution gradually to become large concentration. Basic and the feedstock solution of the resin of this moment is in balance and hydroxylammonium ion and has represented resin balancing capacity to the hydroxylammonium ion in the presence of overfeeding solution in the loading on the cationic ion-exchange resin.
Above-mentioned the second makes cationic ion-exchange resin load the ability maximization of hydroxylammonium ion with the method that the hydroxylammonium ion loads cationic ion-exchange resin, but produces the not purification effluent that contains a large amount of required hydroxylammonium ions. If need, this material stream can be recycled in the feed steam.
Preferably the concentration of hydroxylammonium ion in effluent reaches minimum in ion-exchange step, makes simultaneously the loading maximization of hydroxylammonium ion on cationic ion-exchange resin. This is by such as United States Patent (USP) 5,762, and 897 described careful monitorings are finished from the various parameters of the outflow material flow of ion exchange column outflow in ion-exchange step, and this patent is incorporated herein by reference comprehensively.
As previously mentioned, the purity of gained HA product and concentration depend on the temperature that resin column is kept in whole technical process. Contain have an appointment 10-20ppb or still less the azanol product of impurity metal ion only can maintain 40-100 ℃ at ion exchange resin column, preferably obtain during about 70 ℃ of about 50-.
The feeding line speed that enters ion exchange resin column and pass through therein is generally 2.0-5.0 cm/min. If feeding line speed does not maintain under this value, then can not reach the maximum of hydroxylammonium ion on resin material and load.
Load on cationic ion-exchange resin in the ion exchange column that can be used for the inventive method and usually be the granular form of particle or spherical-shaped beads. There is the space in the result between particle, these spaces are occupied or combination by any fluid that feeds in the ion exchange column in each processing step. In ion-exchange step, the charging that contains hydroxylammonium ion, anionic pollutant and cationic pollutant occupies the space between the cationic ion-exchange resin particle and must rinse out from post before the desorb hydroxylammonium ion from resin. Do like this is in order to prevent the moisture azanol product of anionic pollutant and other charging contaminants substantially pure.
Therefore, the resin that gained is loaded with the hydroxylammonium ion is processed with washings in washing step, from resin, to remove any excessive hydroxylammonium ion, such as HAS solution and ionic impurity (anion and cation impurity), form the resin of the hydroxylammonium ion that is loaded with purification. This washing is usually by United States Patent (USP) 5,762, and the method described in 897 is carried out.
Temperature is kept the washing that improves with concentration
As previously mentioned, must control the temperature of ion exchange column, because the exchange heat release occurs when finally azanol is by the aqueous slkali desorb. This is undertaken by the resin that is loaded with the hydroxylammonium ion of purification with azanol (HA) solution washing gained. The HA aqueous solution is low concentration solution, and it contains 25-34wt%HA usually.
Usually with the linear velocity of 2.0-5.0cm/min HA solution is fed in the ion exchange resin, to contain in the space between the displacement cationic ion-exchange resin particle or the water of combination and form the resin that is loaded with HA. After desorb and rinse step, usually the HA wash solution is recycled by gained HA product.
Have, what should emphasize is that this processing step produces lower temperature in desorption procedure subsequently again, and this can reduce again the decomposition of HA in the production process and finally cause obtaining very pure HA product.
Desorption procedure
The purpose of desorption procedure is that strippant solution is fed in the ion exchange column, this solution comprise will be preferentially at the ion of cationic ion-exchange resin binding site displacement hydroxylammonium ion, thereby with azanol wash-out on this resin and this post. As previously mentioned, useful strippant is preferably monovalence amine alkali, hydroxide bases or its any combination.
Preferred strippant is that concentration is the ammonium hydroxide aqueous solution of the about 55wt% of about 40-. Most preferably concentration is at least 45% ammonium hydroxide aqueous solution. Linear velocity with 1.5-3.5cm/min adds ammonium hydroxide aqueous solution in the ion exchange column of HA solution washing. Importantly keep this low linear velocity of strippant solution, with guarantee with azanol effectively and fully from the cationic ion-exchange resin desorb get off. Also preferred strippant with scheduled volume adds in the ion exchange column of HA solution washing. This consumption depends on used ion exchange resin, strippant and strippant concentration. For example when the 48wt% ammonia spirit with ammonium hydroxide is used as strippant, should in desorption procedure, add the strippant that equals 4.5-4.7 milliequivalent ammonium hydroxide/milliliter resin. Can also regulate the temperature of strippant material stream so that the heat that produces in the desorption process is carried out thermal control.
When desorption procedure finishes, ion exchange column contain enough desorbent material with in connection with the desorb from the cationic ion-exchange resin of hydroxylammonium ion get off. Yet the desorb dosage that adds in the ion exchange column is usually very little, and azanol does not appear in the outflow material flow of ion exchange column usually when adding strippant in the ion exchange column. Therefore, must with rinse step promote strippant by exchange column with azanol from the cationic ion-exchange resin fully desorb get off and prepare out cationic ion-exchange resin for subsequently ion-exchange step.
Rinse step
Rinse step has two effects. It shifts out azanol and enters outflow material flow from ion exchange column from exchange column, it also prepares out ion exchange column for the ion-exchange step of sequence subsequently. The most important aspect of controlling this rinse step is to determine when to begin to collect the ion-exchange effluent material apoblema that contains azanol and when stop to collect the ion-exchange that contains azanol to flow out the material apoblema so that the amount of azanol product and concentration reach maximum, makes simultaneously any pollutant in the collected product minimum. Have been found that by careful control rinsing parameter such as rinsing temperature and linear velocity and parameter such as density, electrical conductivity and pH by monitoring ion-exchange effluent material stream, can make purity reach maximum and make the concentration in the outflow material flow that azanol flows out by ion exchange column in rinse step also reach maximum.
Preferred rinse step serviceability temperature is carried out for the about 30 ℃ deionized water of about 15-. The warm water increase is not used dynamics and the dissolubility of strippant and is improved desorption kinetic yet. The linear velocity that feeds the washings in the ion exchange column in rinse step should be maintained the about 5.0cm/min of about 2.0-.
Preferably in flowing out material flow once detecting in rinse step, the collect outflow material flow of self-exchange post of azanol. This is undertaken by density, electrical conductivity and/or ion exchange column bed height and/or the outflow material flow pH that measures effluent, and such as United States Patent (USP) 5,762,897 is described.
Cationic ion-exchange resin can be used for the inventive method with the fixed bed form of dense compactness, and this bed alternately contacts with desorbent material with incoming mixture. In the simplest embodiment of the present invention, ion exchange resin is used for semicontinuous method with single static bed form. In another embodiment, with two or more, preferred 4 Static Ion Exchange resin beds are combined with suitable valve, so that feedstock solution can by one or more beds that contain ion exchange resin, make strippant solution by one or more remaining static beds simultaneously. Flowing of feedstock solution and strippant solution can be passed through resin bed up or down. In addition, any conventional equipment for the contact of static bed fluid-solid can be used for carrying out the inventive method.
Preferably counter-flow moving bed or simulation moving-bed counter-current flow system is used for the inventive method, has much bigger separative efficiency because they are compared with fixed absorbent bed system. In moving bed or simulated moving bed technology, the sorption and desorption operation is carried out continuously, thereby allows to produce continuously extract and raffinate material stream and use continuously simultaneously feed steam and strippant material stream. Raffinate material stream comprises feed impurities, strippant etc. and is equivalent to outflow material flow from effluent and the water-washing step of above-mentioned ion-exchange step.
A preferred embodiment of the method is utilized the system of simulation moving-bed counter-current flow system that is known in the art, and it is described in United States Patent (USP) 5,762 in general manner, in 897, but has changed number of regions.
When gained HA product contains NH3Pollutant is such as 2-3wt%NH3The time, by with NH3Stripping from this solution and process this HA product. Stripping can be by realizing with nitrogen wash or by carry out coupling vacuum stripping under the vacuum of 35-45 ℃ and 60-15mm Hg.
In order to be used for the semi-conductor industry of requirement metallic impurity＜5ppb, use aftertreatment technology.Remove the ordinary method of metal ion and utilize Zeo-karb.Yet,, may need the Zeo-karb of several types and use multistep method in order to obtain high-purity product.Have been found that metal chelator such as CDTA (hexanaphthene diamino tetraacethyl) and other reagent are effective to complexation of metal ions in the presence of highly spissated HA solution.In addition, sequestrant is electronegative.
Therefore, these complex compounds and metal ion can use anionite-exchange resin to remove from HA solution.Ordinary method can be used to purify refrigerant such as propylene glycol, described refrigerant is used to cool off the HA process stream with safety operation HA method.
In addition, with NH
4The common strong-acid cation-exchange resin of type is as Rohm ﹠amp; Haas Amberjet1500 is used for removing basic metal such as Na and K in the presence of highly spissated HA, does not use H and can not produce
+The difficult problem of type Zeo-karb (they produce many heat, thereby cause that HA decomposes fast).
Embodiment
" long (PFA) post (contains 485cm to use 1 inch ID * 37.7
3Rohm ﹠amp; HaasAmberjet 1500 trade mark resins), embodiment 1 and 2 explanation the present invention.With resin with 40% sulfuric acid pre-treatment removing the metal on the resin, and use 14% NH
3The aqueous solution is exchanged into NH
4 +Type.With the HAS aqueous feed of 35wt% with 16cm
3The flow velocity of/min pumped in the post through 14 minutes.Then with 17cm
3The flow velocity washing of/min 54 minutes.After washing finishes, with the HA aqueous solution (34wt%) of recirculation with 16cm
3/ min infeeded in the post through 8 minutes, then with 17cm
3The flow velocity of/min was introduced NH through 5 minutes
3The aqueous solution (45wt%).Then immediately with 16cm
3The flow velocity of/min is used water rinse 53 minutes.Collected effluent materials flow sample in per 2 minutes.With HA and NH in the product recovery zone
3Concentration bed volume is mapped, curve is shown among Fig. 1.As a comparison, carry out test operation under above-mentioned universal program, different is the HA solution that does not add recirculation.Contrast has and does not have the effluent production concentration of recirculation HA, as shown in Figure 2.Inner column temperature is shown among Fig. 3 because of the reduction of recirculation HA solution.
As shown in Figure 1, need not the pure products that enrichment step obtains 48-50wt% or more HA.
Embodiment 3-6
According to embodiment 1 and 2 described universal programs, use 4 inches PFA lining post.HAS charging flow velocity is 240cm
3/ min, washing and rinse water flow velocity are 240cm
3/ min, recirculation HA flow velocity is 220-240cm
3/ min and moisture NH
3Flow velocity is 160-220cm
3/ min.With HAS charging 16 minutes, will wash respectively simultaneously and rinse water charging 52 minutes and 50 minutes.Use weighing device to monitor and be used for recirculation HA and moisture NH
3Weight.The parameter that is used for these embodiment is summarized in following table 1.
Table 1 uses the HA product yield efficient of single 4 inches PFA lining posts
| Embodiment | 3 | 4 | 5 | 6 |
| Resin volume (cm 3) | 8617 | 8770 | 8641 | 8641 |
| The HA (g) that loads | 568.7 | 578.8 | 570.3 | 570.3 |
| Recirculation HA (g), 34% | 2240 | 2220 | 2210 | 2200 |
| Moisture NH 3(g)，50％ | 1330 | 1361 | 1330 | 1283 |
| Product (49%), cm 3 | 1006.6 | 980.85 | 1017.2 | 910.2 |
| g | 1115.0 | 1066.5 | 1114.3 | 993.3 |
| Clean HA (g) | 546.4 | 522.6 | 546.0 | 486.7 |
| Recyclable materials (40%HA, 2-3%NH 3)，cm 3 | 433.0 | 538.1 | 375.0 | 767.9 |
| g | 459.8 | 501.3 | 416.4 | 777.3 |
| Clean HA (g) | 183.9 | 200.0 | 166.5 | 310.1 |
| Recirculation HA (23-34%), cm 3 | 1438.5 | 1653.6 | 1200.1 | 1079.1 |
| g | 1526.6 | 1718.5 | 1284.5 | 1141.2 |
| Clean HA (g) | 458.0 | 378.1 | 436.7 | 365.2 |
| Total recyclable HA (g) | 1188.3 | 1100.7 | 1149.2 | 1162.0 |
| The clean HA (g) that produces | 242.8 | 145.9 | 231.3 | 103.9 |
| Efficient (%) | 42.7 | 25.2 | 40.6 | 18.2 |
Collected effluent materials flow sample in per two minutes to carry out chemical identification and analysis, per minute is collected product to measure production concentration and productive rate simultaneously.The product that four embodiment collect is listed in following table 2, and HA and NH in the product sample
3Concentration be shown among Fig. 4.According to the production concentration curve, the sample of pure HA average out to 48-50wt% is merged into the product fraction.The product sample that on average contains the pure HA of 22-34% is collected as recirculation HA fraction.With last average HA is 40% and NH
3For the sample of 2-3wt% is merged into the recyclable product of potential HA.
Product (the cm that table 2 per minute is collected
3)
| Embodiment | 3 | 4 | 5 | 6 |
| The product @ time (min) of collecting | ||||
| 95 | 242.11 | 207.52 | ||
| 96 | 243.71 | 246.28 | 199.25 | |
| 97 | 217.76 | 251.64 | 230.68 | 206.57 |
| 98 | 207.85 | 244.97 | 232.28 | 227.4 |
| 99 | 176.98 | 245.56 | 224.85 | 238.34 |
| 100 | 156.3 | 231.02 | 211.5 | 230.26 |
| 101 | 193.79 | 203.6 | 205.37 | 225.26 |
| 102 | 192.55 | 230.57 | 193.93 | 228.1 |
| 103 | 199.95 | 230.79 | 192.96 | 226.54 |
| 104 | 213.93 | 245.4 | 192.96 | 263.2 |
| 105 | 187.48 | 258.68 | 203.36 | 243.5 |
| 106 | 212.71 | 245.98 | 203.89 | 261.24 |
| 107 | 207.34 | 224.63 | 209.82 | 253.67 |
| 108 | 225.66 | 313.42 | 199.15 | |
| 109 | 197.18 | |||
| 110 | 207.96 | |||
| 111 | 186.15 | |||
| 112 | 188.8 |
An object of the present invention is to provide the method that a kind of production has highly purified spissated hydroxylamine free acid.5 pairs of initial charge of analyzing among the embodiment 3-6 by (ICP-AES) of following table are summed up with the result of the HA product that is produced with per 1,000,000,000 parts umber (ppb) expression.This table has illustrated the present invention is produced the concentrated HA of the metal that contains the ppb level by the HAS charging of the metal that contains the 1ppm concentration of having an appointment ability.
Table 5 high purity HA produced according to the invention
| The HAS charging | Embodiment 3 | | Embodiment 5 | Embodiment 6 | |
| Metal content (ppb) | |||||
| Ca | 710 | ＜10 | ＜10 | ＜10 | ＜10 |
| Fe | 850 | ＜10 | 52 | 73 | 70 |
| Na | 1200 | ＜10 | 60 | 11 | ＜10 |
Embodiment 7-13
To contain HA and the concentration that concentration is 38-42wt% is the NH of 2-3wt%
3Recyclable product fraction transfer in 2 liters of rotary evaporators.For these embodiment, at first in about 1200-1400g solution, add 70ppm CDTA stablizer, and it is transferred in the described vaporizer.Use mechanical pump this system of finding time, cool off condenser in the vaporizer with about 4 ℃ water coolant simultaneously.When stripping process finished, the concentration of HA also increased a little.The results list of stripping test is in following table 3.The product of the HA that merging is reclaimed from the product fraction with by stripping process, clean product efficient remarkable increase as shown in table 4 below.
Table 3 is by by NH
3The product fraction coupling vacuum stripping NH that pollutes
3
| The embodiment sequence number | Initial HA (wt%) | Initial NH 3(wt％) | Initial weight (g) | Clean HA (g) | Whole HA (g) | Whole weight (g) | Gross weight (g) |
| 7 | 41.89 | 3.13 | 1173 | 491.5 | 53.97 | 882 | 881.5 |
| 8 | 41.89 | 3.13 | 1235 | 517.22 | 53.45 | 848 | 1729.7 |
| 9 | 39.48 | 1.97 | 1350 | 532.98 | 55.83 | 733 | 4451.5 |
| 10 | 39.48 | 1.97 | 1239 | 489.32 | 52.67 | 760 | 5211.1 |
| 11 | 39.24 | 2.696 | 1350 | 529.7 | 47.91 | 1060 | 9732 |
| 12 | 39.24 | 2.696 | 1163 | 456.17 | 50.07 | 835 | 10567 |
| 13 | 39.24 | 2.696 | 1229 | 482.34 | 49.33 | 913 | 11479 |
| The embodiment sequence number | Eventually clean HA (g) | Condensation product HA (%) | Condensation product NH 3(％) | Condensation product (wt) | HA reclaims (%) | Temperature (℃) | Vacuum tightness (torr) | Time (minute) |
| 7 | 475.75 | 13.63 | 1.193 | 253.8 | 103.83 | 37-38.5 | 66-12.7 | 90 |
| 8 | 453.36 | 13.63 | 1.193 | 213.5 | 93.28 | 37-38 | 62-12.9 | 90 |
| 9 | 409.46 | 12.61 | 1.106 | 412.2 | 86.58 | 37-38 | 62-12.8 | 140 |
| 10 | 400.08 | 12.61 | 1.106 | 382.8 | 91.63 | 37-38 | 52-12.9 | 120 |
| 11 | 507.8 | 9.65 | 1.2 | 346.7 | 102.18 | 38-39 | 70-13 | 120 |
| 12 | 417.88 | 11.5 | 1.2 | 279.7 | 98.66 | 38.5 | 79-13 | 120 |
| 13 | 450.19 | 12.2 | 1.2 | 264.5 | 100.02 | 35-38.5 | 70-13 | 120 |
Table 4 uses the raising of single 4 inches PFA lining posts to HA product yield efficient
| Embodiment | 3 | 4 | 5 | 6 |
| Resin volume (cm 3) | 8617 | 8770 | 8641 | 8641 |
| The HA (g) that loads | 568.7 | 578.8 | 570.3 | 570.3 |
| Recirculation HA (g), 34% | 2240 | 2220 | 2210 | 2200 |
| Moisture NH 3(g)，50％ | 1330 | 1361 | 1330 | 1283 |
| Product (49%), cm 3 | 1006.6 | 980.85 | 1017.2 | 910.2 |
| g | 1115.0 | 1066.5 | 1114.3 | 993.3 |
| Clean HA (g) | 546.4 | 522.6 | 546.0 | 486.7 |
| Recyclable materials (40%HA, 2-3%NH 3)，cm 3 | 433.0 | 538.1 | 375.0 | 767.9 |
| g | 459.8 | 501.3 | 416.4 | 777.3 |
| Clean HA (g) | 183.9 | 200.0 | 166.5 | 310.1 |
| Recirculation HA (23-34%), cm 3 | 1438.5 | 1653.6 | 1200.1 | 1079.1 |
| g | 1526.6 | 1718.5 | 1284.5 | 1141.2 |
| Clean HA (g) | 458.0 | 378.1 | 436.7 | 365.2 |
| Total recyclable HA (g) | 1188.3 | 1100.7 | 1149.2 | 1162.0 |
| The clean HA (g) that produces | 426.7 | 345.9 | 397.8 | 414.0 |
| Efficient (%) | 75.0 | 59.8 | 69.8 | 72.6 |
Embodiment 14-15
Will be according to the hydroxylamine solution NH of above-mentioned embodiment production
4 +Type Zeo-karb (Rohm ﹠amp; Haas Amberjet 1500) handles.This HA solution is stable with the concentration level of 100ppm with CDTA.With this solution with 15cm
3The flow pump of/min is delivered to and is contained 300cm
3Anionite-exchange resin (Rohm ﹠amp; Haas Amberjet 4200) in 1 inch post.With this resin with the sulfuric acid pre-treatment to remove metal, then the Cl type is exchanged into the OH type.Analyze effluent HA with ICP-MS method (embodiment 14).With analytical results and initial HA solution, by Zeo-karb (Rohm﹠amp; Haas Amberjet 1500 (NH
4 +)) effluent and 18Megohm water compare, and be shown in Table 6.
The icp analysis of the table 6 pair sample that exchange is studied from anionic/cationic is summed up
| Embodiment | 14 | 14 | 15 | 15 | ||
| Sample | 18Megohm H 2O | 57％ HA | The 57%HA that purifies with anionite-exchange resin of the present invention only | Only use Zeo-karb (R﹠H 1500NH 4 +) 57%HA that handles | At first use Zeo-karb (R﹠H 1500NH 4 +) 57%HA that handles | Handle and press subsequently the 57%HA that the present invention handles with Zeo-karb (R﹠H 1500) |
| Metal content (ppb) | ||||||
| Al | ＜0.20 | 40 | 15.45 | 9.71 | ||
| Sb | ＜0.10 | ＜1.00 | ＜1.00 | |||
| As | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Ba | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Be | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Bi | ＜0.10 | ＜1.00 | ＜1.00 | |||
| B | 1.72 | 14.81 | 28.22 | |||
| Cd | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Ca | ＜0.20 | 110 | 20.22 | 85.87 | 61 | ＜10 |
| Cr | ＜0.10 | 0.99 | ＜1.00 | ＜1.00 | ||
| Co | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Cu | ＜0.10 | 99 | 19.11 | 17.29 | ||
| Ga | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Ge | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Au | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Fe | ＜0.20 | 140 | ＜1.00 | 114.17 | 170 | ＜10 |
| Pb | ＜0.10 | 84 | ＜1.00 | 6.72 | ||
| Li | ＜0.20 | ＜1.00 | ＜1.00 |
| Mg | ＜0.29 | 15 | 7.21 | 8.28 | ||
| Mn | ＜0.10 | ＜0.5 | ＜1.00 | ＜1.00 | ||
| Mo | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Ni | ＜0.36 | 5.1 | ＜1.00 | 5.19 | ||
| Nb | ＜0.10 | ＜1.00 | ＜1.00 | |||
| K | ＜0.64 | 330 | 139.81 | 16.17 | ||
| Si | ＜0.50 | ＜1.00 | ＜1.00 | |||
| Ag | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Na | 5.40 | 2500 | 1314.42 | 43.12 | ＜10 | ＜10 |
| Sr | ＜0.50 | ＜1.00 | ＜1.00 | |||
| Ta | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Th | ＜0.10 | ＜1.00 | ＜1.00 | |||
| Sn | ＜0.10 | 0.78 | ＜1.00 | ＜1.00 | ||
| Ti | ＜0.10 | 10.99 | 9.18 | |||
| V | ＜0.20 | ＜1.00 | ＜1.00 | |||
| Zn | 0.32 | 18 | ＜1.00 | 32.59 | ||
| Zr | ＜0.10 | ＜1.00 | ＜1.00 |
The purity that repeats to add complexing agent and can further improve the HA free alkali with the stable again HA of anion exchange process.Use NH
4 +Combining also that type Zeo-karb and anionite-exchange resin are handled is shown in Table 6 (embodiment 15).
Embodiment 16
In the production of HA free alkali, refrigerant such as propylene glycol are used to cool off various process streams.If the metallic impurity height in the refrigerant, then any leakage of refrigerant in containing the process stream that concentrates HA may cause undesirable effect.Several crucial metal to commercially available propylene glycol is analyzed, and adds CDTA and use anion exchange process in this refrigerant after the universal program described in the embodiment 14-15.The metal analysis of the sample of purifying to initial refrigerant with by the present invention the results are shown in the following table 7.As shown in table 7, the sample of handling (PG (USP) /+exchange) with Zeo-karb still contains high-caliber Cu and Fe.Use the inventive method handle at three times (PG (USP) /+/-/-/-exchange) afterwards metal is reduced to＜10 and 140ppb (respectively for Cu and Fe).
The metal content of the sample of commercially available propylene glycol of table 7 and purification
| Sample | The PG that receives (USP) | PG (USP) /+exchange | PG (USP) /+/-exchange | PG (USP) /+/-/-exchange | PG (USP) /+/-/-/-exchange |
| Metal (ppb) | |||||
| Ca | 8800 | 14 | ＜10 | ＜10 | 11 |
| Cu | 3600 | 1200 | ＜10 | ＜10 | ＜10 |
| Fe | 22000 | 10000 | 780 | 210 | 140 |
| Ni | 190 | ＜30 | ＜30 | ＜30 | ＜30 |
| Na | 4500 | ＜10 | ＜10 | ＜10 | 36 |
| Ti | ＜10 | ＜10 | ＜10 | ＜10 | ＜10 |
Embodiment 17
In another embodiment of the present invention, in recycle stream, add the security of stablizer CDTA, and in the product container, add this stablizer to improve the security that product stores and transports with the raising production method.Use the stability of quickening calorimeter (ARC) research hydroxylamine free acid.For the ARC test, about 5g HA is being introduced in this testing laboratory with the HA that contains stablizer with nitric acid washing Pyrex glass testing laboratory and after subsequently with the 18Megohm rinsed with deionized water.Air is enclosed by testing laboratory in the ARC unit, reserve little head space.The thermopair that contacts with its bottom is equipped with in this testing laboratory.Provide heater assembly with the heated sample pond around and make the periphery in this pond remain on the temperature identical with sample pool.After temperature reaches evenly, start computer software programs to treat heat research.In case detect the self-heating of sample, just start heating schedule to keep the adiabatic condition of test sample.Collect the temperature and pressure data and measure self-heating speed.
The research iron metal contents is the 57%HA free alkali of 140ppb in the ARC unit.In similar HA solution, add 100ppm CDTA and also use identical ARC unit to study.As shown in Figure 5 the self-heating rate measurements is compared.This figure illustrates and adds the stability that metal chelator CDTA has improved concentrated HA.
Adding CDTA in recycle stream will make the concentrated HA in the inventive method stable when it is produced.In addition, along with the production that concentrates HA, add CDTA and improve the stability of HA when transportation that has certainly in the future and storage.
Claims (17)
1. a method of producing azanol comprises the steps:
(a) feed water solution that will comprise hydroxylammonium ion and pollutent infeeds in the container that contains at least a Zeo-karb, forms the resin that the hydroxylammonium ion loads;
(b) washing water are infeeded in the described container washing the resin of described loading, thereby remove described pollutent, form the resin that the hydroxylammonium ion of purifying loads, wherein said washing water and the association of this resin;
(c) before, the aqueous solution that will comprise azanol infeeds in the described container replacing the described associating washing water of part at least from the loading resin of described purification, thereby forms the associating resin of hydroxylamine solution in subsequently desorption procedure (d);
(d) moisture strippant is infeeded in the described container so that the desorb from the described associating resin of described hydroxylammonium ion is got off, thereby form the unconjugated aqueous hydroxylamine that contains;
(e) the washing water charging is infeeded in the described container from described container, removing described unconjugated solution, thereby form the pure and spissated aqueous solution that comprises described azanol.
2. as the desired method of claim 1, wherein step (a)-(e) is carried out under 50-70 ℃ column temperature.
3. as the desired method of claim 1, wherein said feed water solution comprises oxammonium sulfate.
4. as the desired method of claim 1, wherein said resin is the sulfonated Zeo-karb.
5. as the desired method of claim 1, wherein said strippant is selected from monovalence amine alkali, monovalence hydroxide bases and composition thereof.
6. as the desired method of claim 5, wherein strippant is an aqueous ammonium hydroxide.
7. as the desired method of claim 6, the ammonia concentration that wherein said ammonium hydroxide has is 40wt% at least.
8. as the desired method of claim 1, wherein said container be ion exchange resin column and described moisture strippant and described rinse water in step (d) and the reduced superficial velocity that adds in the described post (e) be lower than 3.5cm/min.
9. as the desired method of claim 1, comprise that further the metal chelator of 8-dihydroxyl quinoline-2-formic acid and composition thereof is handled described pure and spissated solution with being selected from hexanaphthene diamino tetraacethyl, thiocarbamide, tetramethyl-thiuram disulfide, 4.
10. as the desired method of claim 1, wherein in step (a)-(e), further handle described container cooling off described container, thereby be 10-70 ℃ the temperature maintenance of described container with the refrigerant that is selected from propylene glycol, ethylene glycol, propylene glycol/water, glycol/water and composition thereof.
11. as the desired method of claim 10, wherein before described cooling with being selected from hexanaphthene diamino tetraacethyl, thiocarbamide, 4, the described refrigerant of metal chelator pre-treatment of 8-dihydroxyl quinoline-2-formic acid and composition thereof is so that its bind metal ion pollutent and remove described pollutent from described refrigerant.
12., comprise the steps: as the desired method of claim 1
(a) feed water solution that will comprise hydroxylammonium ion, hydrogen ion, ammonium ion, metal ion and anionic pollutant infeeds in the ion exchange column that contains at least a sulfonated Zeo-karb;
(b) when the specific conductivity of ion-exchange effluent surpasses 200mMhos/cm, stop the charging of feed water solution and begin water is infeeded in the described ion exchange column, thereby obtain the materials flow of first ion exchange column washing effluent;
(c) when reaching 0mMhos/cm, the specific conductivity of described exchange column effluent stops the water charging of step (b);
(d) before, aqueous hydroxylamine is infeeded in the described ion exchange column all basically water with the described water charging of displacement from described post in subsequently desorption procedure (e);
(e) ammonia concentration is infeeded in the ion exchange column at least 40% ammonium hydroxide aqueous solution;
(f) when being enough to the amount of complete desorb azanol, adding stops the charging of described ammonium hydroxide aqueous solution in ion exchange column;
(g) the rinse water charging is infeeded in the ion exchange column;
(h) rise to 1.085g/cm when effluent density
3Collect from the effusive product materials flow of ion exchange column when above, wherein this product materials flow is substantially pure azanol and the aqueous streams that does not contain anionic pollutant substantially;
(i) when being reduced to, effluent density is lower than 1.075g/cm
3The time stop to collect the product materials flow; With
(j) stop rinse water being infeeded in the ion exchange column.
13. as the desired method of claim 12, wherein step (a)-(j) is carried out under 10-70 ℃ column temperature.
14., wherein in step (j), stop the rinse water charging afterwards with circulation technology repeating step (a)-(j) as the method for the desired production azanol of claim 12.
15. as the method for the desired production azanol of claim 14, wherein this method is finished in the continuous simulation moving-bed ion-exchange equipment.
16. as the desired method of claim 1, use the continuous simulation ion-exchange unit, this equipment comprises at least 5 ion-exchange areas, each ion exchange column is loaded with the sulfonated Zeo-karb, and this method comprises the steps:
(a) feed water solution that will comprise hydroxylammonium ion, hydrogen ion, ammonium ion, metal ion and the anionic pollutant of first concentration infeeds in first ion-exchange area, obtains being loaded with hydroxylammonium ionic sulfonated Zeo-karb;
(b) washing water are infeeded in second ion-exchange area, this second ion-exchange area comprises and is loaded with hydroxylammonium ionic sulfonated Zeo-karb, obtains the materials flow of first ion exchange column washing effluent;
(c) aqueous hydroxylamine is infeeded in the 3rd ion-exchange area, the 3rd ion-exchange area comprises and the associating sulfonated Zeo-karb of water, obtains the second ion-exchange effluent materials flow;
(d) ammonia concentration is infeeded in the 4th ion-exchange area at least 40% ammonium hydroxide aqueous solution, the 4th ion-exchange area comprises to associate hydroxylammonium ionic sulfonated Zeo-karb, and collects the effluent of the 3rd ion-exchange area;
(e) the rinse water charging is infeeded in the 5th ion-exchange area, obtain the 4th ion-exchange area product materials flow; With
(f) rise to 1.085g/cm when effluent density
3Collect the 4th ion-exchange area effluent materials flow when above, and reduce to 1.075g/cm in effluent density
3The time stop to collect the 4th ion-exchange area effluent materials flow, obtain the moisture azanol product that has the second azanol concentration and do not comprise anionic pollutant substantially, this second azanol concentration is greater than the first azanol concentration in the described feed water solution.
17., wherein use anionite-exchange resin that the azanol product is carried out aftertreatment according to each desired method in the claim 1,12 or 16.
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| US31765101P | 2001-09-06 | 2001-09-06 | |
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| CN113444082A (en) * | 2020-03-24 | 2021-09-28 | 中山大学 | Hydroxylammonium and/or compound, method for the production thereof and use thereof as energetic material |
| CN112723328B (en) * | 2020-12-17 | 2022-03-11 | 浙江锦华新材料股份有限公司 | Preparation method of high-purity solid hydroxylamine hydrochloride |
| CN112661126B (en) * | 2021-01-05 | 2022-03-11 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine hydrochloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5762897A (en) * | 1996-05-03 | 1998-06-09 | Alliedsignal Inc. | Method for manufacturing hydroxylamine |
| US5872295A (en) * | 1998-02-13 | 1999-02-16 | Concept Sciences, Inc. | Purification of hydroxylamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3145082A (en) * | 1959-12-07 | 1964-08-18 | Dow Chemical Co | Stabilized hydroxylamine and its method of preparation |
| US4147623A (en) * | 1977-10-28 | 1979-04-03 | Allied Chemical Corporation | Hydroxylamine purification via ion exclusion |
| US4202765A (en) | 1977-10-28 | 1980-05-13 | Allied Chemical Corporation | Hydroxylamine purification via cation exchange |
| DE3026293A1 (en) * | 1980-07-11 | 1982-02-18 | Riedel-De Haen Ag, 3016 Seelze | METHOD FOR PRODUCING HYDROXYLAMMONIUM PERCHLORATE |
| DE3608495A1 (en) | 1986-03-14 | 1987-09-17 | Basf Ag | METHOD FOR PRODUCING AQUEOUS SOLUTIONS OF HYDROXYLAMINE |
| US5318762A (en) * | 1992-12-09 | 1994-06-07 | Olin Corporation | Process for treating aqueous solutions of hydroxylamine salts containing excess acid |
| US5788946A (en) * | 1997-07-16 | 1998-08-04 | Ashland Inc. | Purification of hydroxylamine |
-
2002
- 2002-09-03 DE DE60208577T patent/DE60208577T2/en not_active Expired - Lifetime
- 2002-09-03 ES ES02776962T patent/ES2254748T3/en not_active Expired - Lifetime
- 2002-09-03 US US10/487,592 patent/US7172744B2/en not_active Expired - Lifetime
- 2002-09-03 JP JP2003526821A patent/JP4297783B2/en not_active Expired - Lifetime
- 2002-09-03 CN CNB028174453A patent/CN1310830C/en not_active Expired - Lifetime
- 2002-09-03 EP EP02776962A patent/EP1427669B1/en not_active Expired - Lifetime
- 2002-09-03 AT AT02776962T patent/ATE315004T1/en active
- 2002-09-03 KR KR1020047003159A patent/KR100907674B1/en active IP Right Grant
- 2002-09-03 DK DK02776962T patent/DK1427669T3/en active
- 2002-09-03 WO PCT/EP2002/009811 patent/WO2003022738A1/en active IP Right Grant
- 2002-09-09 TW TW091120444A patent/TWI297679B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5762897A (en) * | 1996-05-03 | 1998-06-09 | Alliedsignal Inc. | Method for manufacturing hydroxylamine |
| US5872295A (en) * | 1998-02-13 | 1999-02-16 | Concept Sciences, Inc. | Purification of hydroxylamine |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1427669A1 (en) | 2004-06-16 |
| EP1427669B1 (en) | 2006-01-04 |
| WO2003022738A1 (en) | 2003-03-20 |
| US20040213725A1 (en) | 2004-10-28 |
| KR20040041594A (en) | 2004-05-17 |
| DE60208577D1 (en) | 2006-03-30 |
| US7172744B2 (en) | 2007-02-06 |
| CN1551854A (en) | 2004-12-01 |
| TWI297679B (en) | 2008-06-11 |
| ATE315004T1 (en) | 2006-02-15 |
| JP4297783B2 (en) | 2009-07-15 |
| DK1427669T3 (en) | 2006-03-27 |
| JP2005506944A (en) | 2005-03-10 |
| DE60208577T2 (en) | 2006-07-06 |
| ES2254748T3 (en) | 2006-06-16 |
| KR100907674B1 (en) | 2009-07-14 |
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